CN106824191B - Bimetallic catalyst prepares the application in 1,3- propylene glycol in hydrogenolysis of glycerin - Google Patents
Bimetallic catalyst prepares the application in 1,3- propylene glycol in hydrogenolysis of glycerin Download PDFInfo
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- CN106824191B CN106824191B CN201510882004.1A CN201510882004A CN106824191B CN 106824191 B CN106824191 B CN 106824191B CN 201510882004 A CN201510882004 A CN 201510882004A CN 106824191 B CN106824191 B CN 106824191B
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 235000011187 glycerol Nutrition 0.000 title claims abstract description 29
- 238000007327 hydrogenolysis reaction Methods 0.000 title claims abstract description 24
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 title description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 6
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 5
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 230000009467 reduction Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 229910015711 MoOx Inorganic materials 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 229910003091 WCl6 Inorganic materials 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 4
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Chinese gallotannin Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 10
- 238000005470 impregnation Methods 0.000 abstract description 5
- 238000001354 calcination Methods 0.000 abstract description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 abstract description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- BRARRAHGNDUELT-UHFFFAOYSA-N 3-hydroxypicolinic acid Chemical compound OC(=O)C1=NC=CC=C1O BRARRAHGNDUELT-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000003225 biodiesel Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- -1 polypropylene terephthalate Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- YJUUZFWMKJBVFJ-UHFFFAOYSA-N 1,3-dimethylimidazolidin-4-one Chemical compound CN1CN(C)C(=O)C1 YJUUZFWMKJBVFJ-UHFFFAOYSA-N 0.000 description 1
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- 229910017107 AlOx Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- CMDGQTVYVAKDNA-UHFFFAOYSA-N propane-1,2,3-triol;hydrate Chemical compound O.OCC(O)CO CMDGQTVYVAKDNA-UHFFFAOYSA-N 0.000 description 1
- LGUKXHPIRLIAGC-UHFFFAOYSA-N propane-1,3-diol;propane-1,2,3-triol Chemical compound OCCCO.OCC(O)CO LGUKXHPIRLIAGC-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Abstract
The patent is related to bimetallic catalyst and prepares application in 1,3-PD in hydrogenolysis of glycerin, and a kind of hydrogenolysis of glycerin prepares catalyst of 1,3-PD and preparation method thereof, and catalyst is by WOxCarrier loaded active component molybdenum oxide and platinum are constituted.The preparation method of catalyst include: a) solvent-thermal method preparation catalyst carrier WOx;B) the precursor solution incipient impregnation WO of platinum is usedxThen it is dried in vacuo and restores, obtain Pt/WOx;C) by Pt/WO obtainedxIncipient impregnation metamolybdic acid ammonium salt solution obtains final catalyst MoO after drying, calcining reduction againx‑Pt/WOx.Catalyst obtained by the patent, can make glycerine water solution certain Hydrogen Vapor Pressure and at a temperature of with high selectivity hydrogenolysis generate 1,3-PD.
Description
Technical field
The present invention relates to the catalyst that a kind of hydrogenolysis of glycerin prepares 1,3-PD, specially WOxCarrier loaded active group
Divide molybdenum oxide and platinum.
The invention is related to the preparation method and applications of above-mentioned catalyst, specially prepares WO using solvent thermal processx, adopt
Active component platinum and molybdenum are supported with two step infusion processes, and are investigated under different preparation conditions the catalyst and prepared 1 in hydrogenolysis of glycerin,
Activity and selectivity in 3-propanediol.
Technical background
With the rapid development of biodiesel, the by-product glycerin produced in biodiesel process is excessive, converts sweet
Oil preparation high value chemicals becomes the effective means for promoting Biodiesel economy.Glycerol can be raw by hydrogenolysis
At 1,3-PD, 1,2-PD etc., wherein 1,3-PD is the important of production polypropylene terephthalate (PTT)
Monomer.PTT is a kind of new type polyester fiber with biodegradability, it overcomes polyethylene terephthalate
(PET) too hard and too soft polybutylene terephthalate (PBT) (PBT) disadvantage, while there is excellent resilience, chromatophilia is raw
Object degradability etc., thus there is huge development potentiality in industries such as carpet, Textile Engineering plastics.The work of 1,3- propylene glycol at present
Industry production method has the oxirane carbonyl hydrogenation method of Shell company and the acrolein hydration of Degussa and Dupont company
Hydrogenation method.
Oxirane carbonyl hydrogenation method (Chinese patent CN1201407A) using ethylene oxide under cobalt-base catalyst with
Synthesis gas generates 3-HPA, then 3-HPA and hydrogen are hydrogenated to 1,3-PD under hydrogenation catalyst effect
Method.Acrolein hydration method (Chinese patent CN93114516.3) is taken off under solid acid catalyst using gaseous state glycerol hydrate
Water generates methacrylaldehyde, and the methacrylaldehyde of generation is lauched symphysis into 3-HPA, the 3- hydroxyl third of generation in acidic catalyst effect
Aldehyde is under conventional hydrogenation catalyst plus hydrogen prepares 1,3-PD, while by-product 1,2-PD.
Above-mentioned industrial manufacture process is complicated, and environmental pollution is serious, and gained 1,3-PD contains impurity, need to further purify
Processing.
Document (Appl.Microbiol.Biotechnol.1992,36,592-597) reports a kind of use
The method that Clostridiurn strain bio conversion prepares 1,3-PD can turn the glycerite of 110g/l after 29h
Change obtains the 1,3-PD of 56g/l, and this method is influenced by biological metabolic activities, and production efficiency is low, and due to
Production concentration is low, and energy consumption needed for purifies and separates 1,3-PD is also very high.
Document (Catal.Commun.2008,9,1360-1363) reports one kind in 1,3- dimethyl-2-imidazolinone
For under solvent, the method that hydrogenolysis of glycerin prepares 1,3-PD, the yield of the method 1,3-PD is 24%.
The Tomishige seminar of Japan reports the Rh/SiO of Re modification2And Ir/SiO2Catalyst, author is in Ir-Re/
SiO2Fluid sulphuric acid (H is added under catalyst action+/ Re=1), initial hydrogen pressure 8MPa, at 120 DEG C of reaction temperature, 20%
After reacting 36h in glycerine water solution, the yield for having obtained 1,3-PD is up to 38.0%.Subsequent literature (Journal of
Molecular Catalysis A:Chemical.2014,388,177-187) third auxiliary agent especially Ru is also reported to sweet
The facilitation that oily hydrogenolysis prepares 1,3- propylene glycol is most obvious.
The Jinho Oh of South Korea reports the ZrO that Pt is supported on sulfuric acid acidification2On, using DMI as reaction medium, in hydrogen
Initial pressure is 7.3MPa, reacts at 170 DEG C of reaction temperature and has obtained the yield of 1,3-PD for 24 hours and be up to 55.6%.
Organic solvent is used in above-mentioned reaction as reaction medium, and the method for used adding liquid acid, no
Meet the requirement of Green Chemistry.
The direct hydrogenolysis of glycerol prepares 1,3-PD and has obtained very big concern in recent years, because its simple process, raw material are honest and clean
Valence.Document (Chin.J.Catal.2012,33:1257-1261) is although report a kind of mesoporous WO of simple Pt/3It is directly used in
The catalyst of hydrogenolysis of glycerin 1,3-PD, but the whole yield of 1,3-PD is still lower.So far, document
It is 100% and the best performance of selectivity up to 66% that (ChemSusChem2013,6,1345-1347), which reports conversion ratio,
Pt/WOx/ AlOOH catalyst system.But be converted into the unit noble metal catalyst unit time acquisition 1,3-PD yield and
Speech, is still in reduced levels.Simultaneously also have document (Journal of Molecular Catalysis A:
Chemical.2015,398,391-398) report WOxTo Pt/Al2O3Facilitation.Document (Chem.Lett.2012,
41,1720--1722) report AlOxTo Pt Nanoparticles/WO3Make in the promotion of hydrogenolysis of glycerin 1,3- propylene glycol
With.Even author has also investigated MoOxTo Pt Nanoparticles/WO3Facilitation, unfortunately, in this document,
MoOxAddition so that entire catalyst is not exhibited any activity instead.The facilitation and WO of possible auxiliary agentxStructure and Pt
Dispersibility has substantial connection.Entire catalyst system is made a general survey of, research hotspot is concentrated mainly on Pt/W/Al at present2O3System and towards auxiliary agent
Addition direction is developed.Either improve the pattern of each species, content or crystalline structure are arranged auxiliary agent type, there are different journeys
The raising of the 1,3-PD yield of degree, reaction dissolvent are also generally fixed to the water phase condition of environmental protection, but all also keep substantially
In higher pressure (5MPa is in the majority, highest 8MPa) and higher temperature (180-200 DEG C).In order to make the direct hydrogenolysis preparation of glycerol
1,3-PD reaction condition is milder, and yield further increases, it is necessary to new catalysis is further developed on the basis of existing
System.
Summary of the invention
The present invention provides a kind of direct hydrogenolysis of glycerol and prepares catalyst of 1,3-PD and preparation method thereof, with existing skill
Art is compared, which effectively reduces reaction condition and improve the selectivity of 1,3-PD, reduces 1,2-PD
Generation.
The invention patent provides the catalyst that a kind of hydrogenolysis of glycerin prepares 1,3-PD, and catalyst carrier is that hydro-thermal method is closed
At WOx, active component MoOxAnd platinum.Active component MoOxMass content with Pt be respectively 0.001%-10% and
0.01%-10%.
The carrier WO of catalyst of the present inventionxThe preparation method comprises the following steps:
By 3 grams of WCl6It is dissolved in 100mL dehydrated alcohol, to WCl6Yellow transparent solution is transferred to after being completely dissolved and is had
In the water heating kettle of liner, this water heating kettle is placed into 36h in 160 DEG C of preheated baking ovens, then cooled to room temperature, filtered
Successively washed for several times with dehydrated alcohol and deionized water afterwards, be then placed in 50 DEG C of vacuum ovens it is dry carrier WOx。
MoO is prepared using step impregnation methodx-Pt/WOxCatalyst.WO is impregnated with platinum acid chloride solution firstxSupported carrier is living
Property component Pt, after being dried in vacuo 6-12 hours at 50 DEG C, restored 0.5-5 hours at 100~600 DEG C, Pt/WO be madexCatalysis
Agent.Then by Pt/WOxCatalyst is added in metamolybdic acid ammonium salt solution, dry 6-12 hours under the conditions of 120 DEG C, then in 100~
Calcining reduction 0.5-5 hours at 600 DEG C, final catalyst MoO is madex-Pt/WOx。
Catalyst be applied to glycerine water solution hydrogenolysis prepare 1,3-PD reaction in, reaction condition is as follows: reaction be
It is carried out in intermittent tank reactor, glycerine water solution mass concentration is 1-100%, and reaction temperature is 100~300 DEG C, preferably
It is 120~180 DEG C, Hydrogen Vapor Pressure 0.1-10MPa, preferably 0.5~7MPa, glycerol and catalyst reaction time are 0.5-50
Hour, preferably 6-24 hours.
Compared with prior art, the present invention the selectivity that hydrogenolysis of glycerin prepares 1,3-PD can be significantly improved, improve
Glycerol conversion yield effectively inhibits the generation of 1,2-PD.
Specific embodiment
Embodiment 1
The catalyst used is WOxCarrier loaded active component MoOxAnd platinum.Catalyst group becomes Pt%=2%, MoOx%
=0.1%, remaining is WOxCarrier.WOxCarrier is prepared using solvent-thermal method, and specific preparation step includes:
A) by 3 grams of WCl6It is dissolved in 100mL dehydrated alcohol, to WCl6Yellow transparent solution is shifted rapidly after being completely dissolved
Entering in the water heating kettle with liner, this water heating kettle places 36h in 160 DEG C of preheated baking ovens, then cooled to room temperature,
Successively washed for several times with dehydrated alcohol and deionized water, be then placed in 50 DEG C of vacuum ovens it is dry carrier WOx, 2.5 < X < 3.
B) by platinum acid chloride solution incipient impregnation to WOxOn carrier, room temperature is dried in the shade, and the loading of Pt is 2%, 50 DEG C of baking ovens
After being dried in vacuo 6h, Hydrogen activation, activation condition is 300 DEG C, Hydrogen Vapor Pressure 0.1MPa, hydrogen gas space velocity 3600h-1, activation
Time is 1h, then by 2%Pt/WO obtainedxIncipient impregnation metamolybdic acid ammonium salt solution again, MoOxTheoretical loading be set as
0.1%.Batch reactor is selected, glycerine water solution mass concentration is 5% (the total 12g of solution), and catalytic amount is 0.3g (catalysis
Agent and qualities of glycerin ratio are 1:2), reaction temperature is 140 DEG C, reaction pressure 1MPa, reaction time 12h.
Embodiment 2
Change MoOxLoad capacity be 0.05%, other conditions are same as Example 1.
Embodiment 3
Change MoOxLoad capacity be 0.2%, other conditions are same as Example 1.
Comparative example 1
Without MoOx2%Pt/WOxCatalyst, other conditions are same as Example 1.
Examples 1 to 3 and the direct hydrogenolysis of 1 glycerine water solution of comparative example prepare 1,3-PD and are listed in table 1, according to embodiment
1 and 2,3 comparisons, MoOxBest loading be 0.1%.Embodiment 1 be free of MoOxCOMPARATIVE CATALYST it is found that load regulation two
Component MoOxCatalyst afterwards shows very excellent selection in the reaction that glycerol selection hydrogenolysis prepares 1,3- propylene glycol
Property and higher conversion ratio.The present invention is directed to illustrate MoOxTo with the carrier of solvent structure and the Pt/WO that impregnatesxCatalyst
There is facilitation, is conducive to raising hydrogenolysis of glycerin and prepares 1,3-PD selectivity.
1 hydrogenolysis of glycerin of table prepares the catalytic performance comparison of 1,3- propylene glycol
* other include a small amount of methane, ethane, propane, methanol, ethyl alcohol, ethylene glycol, overall conservation of matter.
Claims (5)
1. bimetallic catalyst prepares the application in 1,3-PD in hydrogenolysis of glycerin, it is characterised in that: the catalyst is with WOx
For carrier, 2 < x < 3, active component MoOxAnd platinum, wherein 2 < x < 3;Wherein the content of Pt is catalyst weight
0.01%-10%, MoOxContent be catalyst weight 0.001%-10%;
The carrier WOxIt is prepared using solvent-thermal method, detailed process are as follows:
By 1-3 grams of WCl6It is dissolved in 100-200mL dehydrated alcohol, is transferred in water heating kettle after being completely dissolved, and in 120-180 DEG C
12-600h is placed in baking oven, is cooled to room temperature suction filtration, washing, dry carrier WOx;
The bimetallic catalyst is prepared using infusion process, detailed process are as follows:
1) WO is impregnated with platinum acid chloride solution firstxSupported carrier active component Pt, after 4-36 hours dry at 40-140 DEG C, Yu Qing
It is restored 0.5-10 hours at 100 ~ 600 DEG C of gas atmosphere, obtains Pt/WOx;
2) then by Pt/WOxIt is added in metamolybdic acid ammonium salt solution, after 4 ~ 36 hours dry at 40-140 DEG C, is forged at 100 ~ 600 DEG C
It burns and restores 0.5-10 hours, final catalyst MoO is madex-Pt/WOx。
2. application according to claim 1, it is characterised in that:
Platinum acid chloride solution molar concentration 0.05-10M, metamolybdic acid ammonium salt solution molar concentration 0.05-10M.
3. application according to claim 1, it is characterised in that: reduction temperature is 300 ~ 400 DEG C.
4. application according to claim 1, it is characterised in that: the catalyst prepares 1,3-PD for hydrogenolysis of glycerin
In reaction, reaction raw materials are glycerite, mass concentration 1-100%, Hydrogen Vapor Pressure 0.1-20MPa, reaction temperature 10
~500℃。
5. application according to claim 4, it is characterised in that: Hydrogen Vapor Pressure is 0.5 ~ 7MPa, and reaction temperature is 120 ~ 180
℃。
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CN108636440B (en) * | 2018-04-16 | 2021-08-10 | 江苏七洲绿色化工股份有限公司 | Catalyst for preparing 1, 3-propylene glycol by hydrogenation of glycerol aqueous solution and preparation method thereof |
CN111229204A (en) * | 2018-11-28 | 2020-06-05 | 中国科学院大连化学物理研究所 | Application of bimetallic catalyst in preparation of 1, 5-pentanediol from tetrahydrofurfuryl alcohol |
CN115709065A (en) * | 2022-11-23 | 2023-02-24 | 西安凯立新材料股份有限公司 | Catalyst for preparing ethylene glycol by dimethyl oxalate hydrogenation, and preparation method and application thereof |
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CN101003462A (en) * | 2007-01-25 | 2007-07-25 | 中国林业科学研究院林产化学工业研究所 | Method for preparing 1,3 propylene glycol by using glycerol method |
CN102728380A (en) * | 2012-05-08 | 2012-10-17 | 中国科学院大连化学物理研究所 | Catalyst used for preparing 1,3-propylene glycol through glycerin hydrogenolysis, preparation method thereof, and application thereof |
CN104582839A (en) * | 2012-08-30 | 2015-04-29 | 国立大学法人大阪大学 | Catalyst for hydrogenolysis of polyhydric alcohol and method for producing 1,3-propane diol by using the catalyst |
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